Method and materials for photographic color imaging

ABSTRACT

COLOR IMAGING METHODOLOGY AND MATERIALS ARE DISCLOSED UTILIZING CYANINE DYE COORDINATE STRUCTURES OF THE TYPE:   ((CYCLOPROPYL-NH-)2-C=N)N-Z (2M)N   WHERE M IS A HEAVY METAL ION AND N IS AN INTEGER, SAID STRUCTURE BEING CHOSEN TO BE LIGHT SENSITIVE TO A SELECTED COLOR COMPONENT OF A LIGHT PATTERN TO BE IMAGED, WHERE   Z IS A DYE COUPLER FOR THE DEVELOPER-COLOR FORMER FRAGMENT $NH AND WHICH WHEN COUPLED WITH SAID FRAGMENT YIELDS A DYE HAVING A DESIRED COLOR RELATIONSHIP TO SAID SELECTED COLOR COMPONENT.

March 26, 1974 J E YOUNG 3,799,776

METHOD AND MATERIALS FOR PHOTOGRAPHIC COLOR IMAGING Filed May 19, 1972 United States Patent US. Cl. 96-2 14 Claims ABSTRACT on THE DISCLOSURE Color imaging methodology and materials are disclosed utilizing cyanine dye coordinate structures of the type:

where M is a heavy metal ion andn is aninteger, said structure being chosen to be light sensitive to a selected color component of a light pattern to be imaged, where Z is a dye coupler for the developer-color former fragment ANH and which when coupled with said fragment yields a dye having a desired color relationship to said selected color component.-

This application is a continuation-in-part of men pending application, Ser. No. 52,820, filed July 7, 1970" now abandoned. I

This invention relates generally to imaging technology, and more specifically relates to methods and materials for color imaging of light patterns.

Virtually all presently employed chemically-based imaging systems, including the trademark-identified systems of Kodacolor (negative), Kodachrome and Ektachrome Reversal (positive), and Polaroid Dye Transfer Reversal color, utilize a so-called monopack tri-emulsion system. These monopack systems are structurally very complex and in particular are typically composed of three superimposed thin emulsion layers, sensitive respectively to blue, green, and red light, plus a suitably interposed yellow dye layer and a plastic support substrate. Each emulsion layer therein contains specific color sensitizers commonly cyanine dyes specific color couplers (to form direct or complementary colors), silver halide crystals, sensitizers, retarders, etc.

In the newer of these conventional color imaging systems, the said color couplers are introduced into the recording emulsion and prevented from migrating by incorporating the coupler in an oil emulsion or resin and suspending small particles of the eiiiulsion oiT'resin throughout each monopack emulsion layer. The color former-developing agent, usually a substituted paraphenylene diamine, is contained in a separately employed color developer solution. The color former-developing agent therefore must diifuse through the multi-layer emulsion, reduce the exposed silver to in turn oxidize the (167 veloping agent,'whereupon the oxidized developing agent couples with the emulsion-contained coupler to form the appropriate dyes. In consequence of such arrangement considerable resolution is lost in current color films, and scattering effected by the aforementioned small additionally has a detrimental eifect on color rendition of the materials.

particles,

Patented Mar. 26, 1974 Developing processes for such conventional color imaging systems are furthermore well-known to be very complex and time-consuming. By way of illustration, and even reducing such processes to their simplest form, at least thefollowing sequentialsteps are involved in development of a conventional positive (reversal) color film: negative silver development; stop washing; white light exposure; dye former development; silver bleach; stopwashing; hypo fixing; and wash and drying.

.. In accordance with the foregoing, it may be regarded as an object of the present invention, to provide processes and materials which vastly simplify both the structuring of color imaging members and the processing techniques for producing color images in an exposed member.

It is afurther object of the present invention, to provide color imaging methods and materials which enable development of color images in exposed members by simple heat, infra-red or radiant energy processing techniques, or -by simple treatment of said memberwith a bulfered aqueous alkaline solution.

It is another object of the present invention, to provide a color. imaging member wherein a single layer in the member may carry commonly the various color-sensitive compounds of the invention, with in situ formation of the dye image occuring in such layer without the use of a migrating dye former-developing agent, whereby a vast improvement in color image resolution and color rendition is enabled.

Now in accordance with the present invention, the foregoing objects, and others as will become apparent in the course of the ensuing specification, are achieved in a color imaging system based upon the use of cyanine dye coordinate structures of the general type:

former fragment ANH. In systems in accordance with the invention the said coordinate structure is chosen to be light sensitive to a selected color component of a light pattern to be imaged, with Z being an appropriate coupler for. ANH such that when coupled therewith a dye results having a desired color relationship to said selected color comp'onentLImpingement of light including said selected color component--i.e. conventional exposure-serves to reduce the metallic ion M and to oxidize the fragment ANH. Thereafter development of the desired dye image may be simply brought about by disrupting-cg. by radiation. or'chemical environment-the chemical bonds joining the developer fragments to the dye coordinate.

struction, whereby the dye coupler Z couples with oxidized developer fragments at points exposed to said selected color component. Because the coordinate structures depicted eifectively carry in a single organic salt form the light sensitizer (and light-sensitive) agent, developercolor former, and dye coupler, production of the ultimately desired dye image is entirely in situ, i.e. in the immediate vicinity of the dye structure (1); thus unlike the practice in conventional color photography no external developing agent need in any way be utilized. The result is avast simplification in developing techniques and in image resolution resulting from development: and

moreover a tri-mix emulsion is enabled, which is to say simultaneously and commonly several or a plurality of W classes of coordinate structures of the aforementioned type sensitive respectively to different color compounds of an incident light image.

In the drawings appended hereto: v

FIG. 1 is a schematic cross-section through a reversal positive monopack color film based upon present invention; and

FIG. 2 depicts in schematic cross-section a color film structure which in accordance with the invention utilizes but a single sensitized layer.

The coordinate structures utilized in accordance with the invention are in an organic structural sense; members of dye sensitizers classified as cyanines, azacyanines, carbocyanines, hemicyanines, and merocyanines, and con-' tain heat or alkaline fracturable members which when released act in the nature of photographic developer-color formers. The fact that these compounds are thus per se dye sensitizers accounts for the fact that no additional agents need be present in imaging members incorporating these coordinate structures to perform the sensitization function.

The said coordinate structures may also, in a structural sense, be regarded as derivatives of the compound guanidine. Considering the structures as such, we may note by way of illustration the action of heat (typically 100 to 200 C.) or alkaline conditions (pH of about to 13) upon a representative triphenyl guanidine:

conditions In this illustration, the symetrically paired double substituted paraphenylene diamines to the left of the carbon atom correspond to the ANH fragment; the group corresponds to the coupler which is more generally represented by Z in the generalized coordinate structure quinone diamine groups. Since quinone groups are in condition to thus couple with the Z-corresponding group' to yield a preselected dye if the Z-group is appropriately chosen. a

More generally in accordance with the invention, the coordination compound silver salt (or silver halide salt) (l) of the cyanine organic dye acts as the sensitive medium, color sensitizer, dye coupler (direct or complementary color), and devolping agent. All of these functions are incorporated in the sensitive layer as one coordination compound. The system can also use other heavy'metals, in addition to silver, as electron traps or redox components.

N( C 2Hs)2 Cyanlne Sensitizer The bracket beneath the structure (2) indicates that the entire structure per se is a cyanine dye sensitizer. The lefthand-guanidine likeportion of the dye coordinate structure may be bonded to the coupler structure Z to provide resonance interaction (conjugated) or in an inert position (unconjugated or blocked) to prevent resonance interaction to provide the desired color in the cyanine sensitizer. In this exemplary structure ANH of structure (1) is shown as a double substituted paraphenylene diamine. While such is indeed a preferred form for ANH it will be appreciated that in general ANH can comprise virtually any of the numerous color former-developing agents known to those skilled in the art of color photography. Thus in more general terms the coordinate structure (2) can be written as:

(a) R R /O=N z I vH R n where It may, among other things, be observed in (3) that the two components corresponding to the ANH in structure (1) can d fie from one another; thus the two ANH fragments in (1) can represent differing developer-color may require cooling to contain the reactants. After the formers. Y initial reaction subsides, attach electric heating mantle Furthermore it will be appreciated that the dye coupler and water cooled condenser. Reflux the mitxure for 8 Z in structure (3), may itself be chosen with enormous hours. Distill off the excess CS and alcohol. Wash residue flexibility, 80 at when coupler Z-which may also be 5 with an excess of dilute HCl (1:10) to neutralize the referred to as a dye intermediate-couples with the residual KOH and remove unreacted para phenylene dicolor former-developer ANH, a dye results which has amine. Filter, wash with warm water, and dry. Purify by specifically desired colorcharacteristics with respect to recrystalization, desolving the residue under reflux in the original actinic radiation which activated the coordiboiling rectified spirits (Ethanol). Filter in heated funnel nate structure. 10 if the solution is not clear. Add hot water until the solution The dyes used herein are by virtue of their dual purpose becomes cloudy, cool, and filter. modified cyanines. Dyes of this general type are elucidated N,N bis (4-dimethylaminophenyl) thiourea is also in the literature and the procedures for synthesis of comavailable commercially as #2239 from: K&K Laborapounds of this type are well-known to those skilled in the tories Inc., Plainview, N.Y. art. Many current processes, for example, for the formulation of cyanine dyes use condensation type reatcions. These EXAMPLE 2 reactions, shown in Mees, C. E. K., The Theory of the (II) Preparation of N,N bis (4-dimethyl- Photographic Process, The Macmillan Co., New York, aminophenyl)carbodiimide 1954, utilize an active hydrogen on one reactant and an Equations:

active negative atom (halogen, cyano, alkyl or aryl mercapto, alkoxy, anilino, or acetanilido) on the other reac- C S gg o CaClz, Reflux tant. Condensing agents are used as scavengers and to 2 excess) Benzene shift the reaction equilibrium in the desired direction. The

intermediates used in the preparation of conventional 02 e t sensitizing dyes, and the condensing agents, including their preparative procedures, are discussed in Glafkides, P., In a 500 balloon flask ITIIX 100 I111- of Photographic Chemistry, vol. I and II, Fountain Press, anhydrous benzene (Baker 9154) l ernate solvents di- London, 1960 starting on page 753. ethyl ether or acetone), 65 g. anhydrous calcium chloride Typically, the dyes described in this patent application (Bak r 4) (alt rnat drying agents: Sodium sulphate can be prepared by the two following exemplary ap- (B r 1), g n Sulphate (Baker 1" proaches, depending upon the substituents in the dye hydrous magfleslllm Carbonate), 5;- Of bis i t di t dimethylaminophenyl) thiourea (from preparation I or (a) by condensation of appropriately substituted guani- K&K Laboratories and 144 of mercuric OXide dines with intermediates containing negative active atoms a er 2620 Or 2630) (alternate desulfllfilation agents! in the desired positions: and (b) by formation of the lead oxide (l3aker 2338) or sodium hypochlorite). Attach appropriately substituted guanidine structure in situ via electric heating mantle and water cooled condenser. Rethe reaction of the substituted carbodiimide with amino flux the mixture for 6-8 hours. Filter to remove sulphides group(s) located in the dye intermediate. and dr'yingagent, distill off excess benzene, and dry. Purify The general scheme pursuant to which synthesis of the by recrystallization from dry benzene. Maintain the comdye sensitizers of the invention may be effected, is set 40 p und in a dry atmosphere to prevent the formation of forth as follows: I urea compounds.

SNYTHETIC FLOW CHART Negative atom l Disubstituted guanidine substituted intermediate Reaction IIIb 7 Reaction V 7 IV Reaggion Reaction I 1 a Substituted 1 Disubstltuted 1 Reaction Dye sensltizer aromatic amine thiourea Reaion II Reactiozf VI Disubstituted carbodiimide Amino substituted 1 intermediate 1 Commercially available chemicals.

Detailed procedures respecting preparation of the said Bis (p-dimethylaminophenyl) carbodiimide is also comsensitizers pursuant to the foregoing flow chart are set mercially available as #12325 from K&K Laboratories forth hereinbelow: 'Inc., Plainview, N.Y. See also Pat. 2,942,025.

EXAMPLE 1 EXAMPLE 3 (I) Preparation of N,N'-bis(4-dimethylamino p y thiourea I V (IIIa) Preparation of N,N bis (4-dimethylaminophenyl) guanidine--from carbodiimide Equations: Equations:

welg t as catalyst Anhydrous Ammonia Gas ((CI-Ia)zNNHz) 0s H23 I Y 0e01,, Benzene In a 500 ml. balloon flask, mix 63.5 ml. 50 g.) absolute G NH E Q NW3) ethyl alcohol, 45 ml. (57 g.) Carbon disulfide (Baker 2630), 132 m1. (136 g.) N,N dimethyl-p-phenylene di- In a500 ml. balloon flask add 25 g. of anhydrous calamine (EK P 2147) and 11.4 g. Potassium Hydroxide cium chloride (Baker 1314) (alternate: sodium sulphate (Baker 3140). An exothermic reaction takes place which (Baker 3891), magnesium carbonateanhydrous, or magnesium sulphate (Baker 2506), 100 ml. (87.9 g.) dry benzene (Baker 9154), and 9 3.5 g. of N,N' bis (4-dimethylaminophen'yl) carbodiimide (from preparation 11 or #12325 from K&K Laboratories Inc.).. A gas dispersion tube with fritted disc or cylinder is introduced into the mixture and anhydrous ammonia gas is allowed to bubble through the liquid at room temperature for 30 minutes. Filter to remove the drying agent and distill olf the benzene exercising care to prevent thermal decomposition of the guanidine. Purify by recrystallization from dry benzene or absolute ethanol.

EXAMPLE 4 (IIIIb) Preparation of N,N' bis (4-dimethylaminophenyl) guanidine-direct from thiourea Equations:

Ca 012, Reflux In a 500 ml. 2 neck balloon flask mix 100 ml. (87.9 g.) of anhydrous benzene (Baker 9154) (alternate solvents: diethyl ether or acetone), 65 g. anhydrous calcium chloride (Baker 1314) (alternate drying agents: sodium sulphate, Baker 3891, magnesium sulphate, Baker 2506, or anhydrous magnesium carbonate), 59.5 g. of N,N bis (4-dimethylarninophenyl) thiourea (from preparation I or K&K Laboratories #2239) and 144 g. of mercurix oxide (Baker 2620 or 2630) (alternate desulfurization agents: lead oxide, Baker 2338, or sodium hypochlorite). A gas dispersion tube with fritted disc or cylinder is introduced through one neck. Attach electric heating mantle and water cooled condenser to other neck, Introduce anhydrous ammonia gas through the gas dispersion tube at a very low rate. Reflux the mixture for 68 hours. Filter, distill off excess benzene exercising care to prevent thermal decomposition of the guanidine. Purify by recrystallization from dry benzene or absolute ethanol.

EXAMPLE (IV) The conversion of N,N' bis (4-dimethylaminophenyl) guanidine to N,N bis (4-dimeth'ylaminophenyl) carbodiimide via nitrous acid Since the carbodiimides are highly reactive reagents and cannot be stored for prolonged periods this reaction is a simple expedient to facilitate the availability of reagents. The disubstituted guanidine can be converted to the corresponding carbodiimide by simply treating the guanidine with nitrous acid at low temperatures.

The removal of ammonia from guanidine, which accomplishes the same result (the formation of the carbodiimide), occurs with 80-90% yield with nitrous acid. See Smith, P.A.S., The Chemistry of Open Chain Organic Nitrogen Compounds, W. A. Benjamin Inc., New York, 1965, p. 258

Since the dyes used herein serve two purposes: both as the sensitizer/ sensitive media and as the coupler/ developer color former there are two major restrictions on their structures:

(1) Sensitizer/sensitive media.-In this sense the dyes must conform to the structural limitations of the cyanine series sensitizing dyes. These limitations can be generalized as follows:

pentavalent trivalent nitrogen nitrogen In which the pentavalent nitrogen is normally contained in a ring structure and the trivalent nitrogen can either be linear (open chain) or contained in a ring structure. In all cases there is an odd number of carbon atoms between the trivalent and pentavalent' nitrogen atoms, with alternating single and double bonds (resonant structures). The structures can be weighted to shift the spectral absorp tion by the addition of vinyl groups between the nitrogen atoms i.e. (OH -CH). It should also be understood that CE is equivalent to and interchangeable with N= therefore some of the atoms in the chain can be nitrogen. The nitrogen containing structures can contain. in addition, atoms of oxygen, sulfur, or selenium provided they are not interposed in the direct chain between the two nitrogen atoms.

Alternately the compounds can also be of the merocyanine family with the following structural restrictions: Merocyanines Keto group In which the trivalent nitrogen and keto groups can be in linear (open chain) or contained in ring structures. In all cases there is an even number of carbon atoms between the trivalent nitrogen and the keto group, with alternating single and double bonds (resonant structures). These structures can be weighted to shift the spectral absorption by the addition of (=CHCH) E groups between the nitrogen and keto structures. It should also be understood that -C= is equivalent to and interchangeable with N= therefore some of the atoms in the chain can contain in addition, atoms of oxygen, sulfur, or selenium, provided they are not interposed in the direct chain between the nitrogen and keto groups.

These structures are resonant between the two extremes shown in the following:

Qyanine N 1'q=( =).s iiE E ).N

Trlvalont Pentavalent Pentavalent; Trivalent Merocyanine Trivalent Pentavalent (2) After exposure and fragmentation of the guanidine structure or portion of the structure the residual coupler structure must be suitable for coupling under alkaline conditions with the oxidized paraphenylene diamine (quinone diimine). The dyes formed in the light struck image areas to produce either the equivalent color (direct positive) or complementary color (negative) image.

Cyan couplers The majority of cyan couplers currently in use are of the phenol class which yield indoaniline dyes.

Including:

l-naphthol l-thionaphthol 2,4-dichloro-1-naphthol naphthols with 2,4,5,6-substituents 3,5-dibromo-o-cresol 4-chloeophenylphenol m-hydroxybiphenyl 5 ,7-dibromo-8-hydroxyquinoline Dihydroxydiphenyl methanes 1hydroxy-2-naphthoyl-ochioranilide p-Niteobenzylpyridinium chloride 3hydroxyguanazopyrazolone Naphthaquinoline (with B substituted auxochrome) Hydroquinone monomethylether I v. R

I Yellow couplers 1 The yellow couplers in current use are of the active methylene compound type which produce azomethine dyes. These-compounds can be generalized by the follow Z=unsaturated group which may be linearor closed ring,

-COR, CEN, or C=ONHR. I The groups of greatest value include:

Acylacetonitriles I r B 0-8 OH2CN Acylacetoamides I o RC-CHz-i'i-NHR 1,3-diketones Carbethoxyitand carbohydra zinoderivatives of, quin; azolone r n a. n v I :i-NH-rNHz N-ethyl ox'indole indanedione-Lli Thioindoxyl 5-chlorocoumaranone-3 Y 1-phenyl-3-methyl-5-pyrazolone S-phenylisoxaiblone-S Pyrimidazololone V v N-phenyl-p B-anlino 'glutaconim ide N-phenylhomophthalimide Oxodiazole v Quinaz olone "Magenta couplers The magenta couplers in current use in l qe the f ll w ing: I u p Phenylactonitriles- Cyanacetylureas Cyanacetylhydrazones I Pyrazolones n.

Indazolones Quinoline Substituted-position' "i V (2) alkyl, aminophenyl, stearoylaminophenyl (4) octadecanesulphonomadophenyl (6) v -ii-OH 'iIi--NHR II 'TOH Upon consideration of the foregoing it will be evident that the best approach to a cyan color is via the mero cyanine structures; The yellow and magenta can easily be accomplished using either cyanine or merocyanine dye structures. 1 I v .;L.:.Preparation of cyanine dye intermediates Many of the intermediates used in the preparation of cyanine dyes are commercially available from suppliers such as: Distillation Product Industries, BK Division of Eastman Kodak Co., Rochester, New York; Aldrich Chemical Company, Inc., Milwaukee, Wis.; J. T. Baker Chemical Co., Phillipsburg, N.-J.;' KK Laboratories, Inc.,

Plainview, -N.Y.; Gallard-Schlesinger Chemical Mfg.

Corp., Carle Place, L.I., N.Y,

,Glat'kides, Pierre, Photographic Chemistry, Fountain Press, London, 1960,:pp. 753-787, contains detail procedures andliterature references for the synthesis of the more common intermediates used in sensitizing dyes and the formation of the dyes themselves.

In the present instance the requirement's are relatively simple, that the intermediate to be condensed with the disubstituted guanidine contain a reactive negative atom or group, in the appropriate position, such as halogen, cyano, alkyl or'aryl 'mercapto, alkoxy, anilino, or acetanilido; In the synthetic process using the'disuibstituted carbodiimide the desired couplingposition must contain an amino group which is easily substituted if 'we have the intermediate with a reactive negative atom or group in the appropriate position. Theformationi of amines by the dis placement of a halogen atom with ammonia is well known tothoseskilledintheart. i

Most of the reactions by which cyaninesv dyes are formed are of the condensation type; two intermediates are allowedto react under suitable conditions and the dye is formed with the elimination of some simple molecule, such as mineral acid, mercaptan, or alcohol, water, aniline, or acetanilide. The intermediates used are of two categories: those containing active hydrogen, which furnish the hydrogen of the simple molecule eliminated in the reaction and. those containing a reactive negative atom or groupsuch as halogen, cyano, alkyl or aryl mercapto alkoxy, anilinopr acetanilido, which groups combine with the reactive hydrogen of the first component.

The commonly used condepsing agents include: trialkylamines, trimethylamine, triethylamine, tri N propyl amine, tri-N-butyl amine, diethylmethylamine, ethyldimethylamine, quinoline, pyridine, isoquinoline, dialkylamines, sodium carbonate,. and potassium carbonate.

In the case where one is reacting the highly reactive carbodiimides with an amino group in the intermediate the following generalization holds: Reactions in which carbodiimides are used are. usually carried out under mild conditions at room temperature, or at a slightly higher temperautre, with the use of suchaccessible solvents as ether, pyridine, or dimethyl formamide. The reactions, as a rule, do not take more than a few hours. K

In terms of economics the,, Guanidine synthesis is muc cheaper as the N,N' bis (pdirnethylaminophenyl) carboodiirnide has a high commercial price. The storage problems associated with carboodiimides are serious since they are highly reactive, teridto polymerize, and therefore have very short shelf lives. As an intermediate in the synthesis of equivalent guanidines, which have long shelf lives, they are convenient.

A synthetic procedure wilhnow be set forth illustrating the guanidine synthesis. The resulting dye is a double merocyanine with bothketo groups contained within a single ring structure. The two groups, are isolated in a g-s n a (V) Guanidine synthesis of a merocyanine dye Condensation product of N,N' bis (4 dimethylaminophenyl) guanidine and 2,5-dichloro-p-benzoquinone 1 Equations:

N,N'bis( f-dlmethylaminophenyl). y guanldine 2, S-dlchlorw-bcnzdqulndde In a 500 ml. balloon flask,-m.ix 100ml. (78.9.;g.) abso: lute ethanol, 59'.4'g.'N,N' bis, -(4-dimethylaminophenyl) guanidine (from preparation I'Ila or -IIIb),. l7.".7--"g. 2,5-di-v chloro-p benzoquinone (EK- 4410), .6 gumagnesium oxide (BA 2477). Attach water cooledcondenser, electric heating mantle, magnetic stirring unit-"and reflux'themixture for..2 hours. Filter torsremove isolids, distillloff ethyl alcohol, wash residue with distilled water, and dry. Purify by recrystallization-from dry-ethanol.

The resultant dyeis magentaicolor in methanol solutions. After forming-the silver salts, exposure, facture of the guani'di'ne portions of the structure, and 'coupling the resultant d'ye is cyan color in methanol'solution.

The formation of 'sil ve'r or "silver halide salts of-these' dy'es follow the conventional methods currently inuse in the manufacture of -silver halide filmt'These'pro'cesses involve the introduction of silver "nitr ate into-the mixture: and subsequent -introduction' of-soluble halide's'al't's (Kl, KBr, KCl, NaI, 'NaBr, N'aCl) -followed by washing'with water.

12 EXAMPLE 7 s The following reaction will' demonstr'ate the technique and simplicity in the formation of cyanine dyes using carbodiimides as reactants. I

The intermediate, 2-amino-quinoline, is obtained from: Gallard schles inger' Chemical Mfg. Corp., Carle Place, L.I., NY. or K&K Laboratories.

The intermediate is.then.converted to a cyclammonium quaternary base in accordance with'the procedures shown at pan-'28sof Glafkides'. The procedures are general and in'this case' we" use CH I-as theal'kyl halide-With this reaction completed-' weproceed as follows:

(VI) Carbodiimide synthesis of a cyanine dye Condensation productof N,N'bis (4-dim'ethylamin0- phenyl) carbodiimide and 2-aminoquinoline methyl iodide.

Equations:

. N ,N bis (4-dlmethylamlnophenyl) earbodllmide [bis(p-dimethylaminophenyl) carbrodiimlde] KdzK Labs #12325 FW 280 In a ml. balloon flask equippedwith a stopper, mix 5 g. of dry calcium chloride (BA 1308): 25; ml. (17.7 g.) of anhydrous ether (BA 9244), 1.0 g. N;N'bis (4- dim eth ylaminophenyl) carbodiimide (K&K;Labs #12325), and 1.0 g. of Z-aminoquinoline methyl iodide (K&K Labs #15089). The mixture is stirred while remaining at room temperature for approximately 2 hours. Filter to remove drying agent, distill off' ether, and dry. Purify by recrys tallization from ethanol.

The initial color of this dye is. approximately magenta. After exposure and'appropriateprocessing' the resultant image is magenta.

Of the vast number of structures of the foregoing type which may thus be used in theinvention, it will be evident that only three arerequired to produce subtractive or additive colors in an imaging member. Th1is, for example,

i a reversal positive monopack (integral t'ripack) color film is structured as shown in FIG. 1. The schematic. cross: section of the member 1 therein is broken at the middle' to depict a first portion (a) illustrating the condition of. member 1 prior to processing, and I a second portion (b) illustrating the condition of member 1 subsequent to processing. From the direction of light exposure (top of figure) the member 1 at portion (a) is thus seen to con sist of a blue light-sensitive layer 2a, yellow filter'layer 4a, a green/blue light-sensitive layer 6a, a red/blue lightsensitive layer 8a, a transparent support 10a, and a dyed anti-halation layer 12a. After processing at (b), the cone sponding structure consists of a .blue. absorbing layer 2b, a clear layer 4b, a green absorbing layer 6b, a red absorbing layer-8b, the support 10, and a clearlayer 12b. It should be obvious that with judicious selection of the dye coupler portion Z of the cyanine sensitizer that either direct of complementary colors can be produced utilizing the same development process. The utilization of a single organic salt cyanine sensitizer as the sensitive s'alt, sensi' tizer, dye former-coupler and dye former-developer,'with in situ formation of the dye image associated with the wavelength portion of the original light image to which a selected coordinate structure is sensitive, now makes possiblea color imaging structure employing but a single sensitive layer. Such a vastly simplified structure 14 is schematically depicted in the cross-sectional view of FIG. 2, and is seen to include a transparent support 15 upon which is coated a sensitive layer 17. The layer 17 includes a clear binder-which may constitute a clear plastic such as polyvinyl alcohol or other permeable resins, in which is dispersed in common a plurality of classes of organic structures of the type set forth herein. Thus in the simplest'case three such classes of coordinate structures are commonly present in layer 17, each of said classes being respectively sensitive to a primary color component of a light image made incident upon member 14. In such simplest case the dye that results after processing each specific class of coordinate structures-dc. after the coupler Z in each class structure couples with its developer-color former fragments ANH--may have color reflective characteristics substantially identical with that color component of the original image to which the said coordinate structure is sensitive. In other cases the resulting dye, however, may be partially or entirely absorbtive of wavelengths corresponding to the actinic wavelengths, selection of appropriate coordinate structures to yield desired dyes being a matter of choice dictated by the color balance characteristics desired in a given system.

In accordance with the present invention, development of exposed members such as those of FIGS. 1 and Z is brought about by the extremely simple technique of heating the members Z (typically to from about 100 to 200 C.) or treating the sensitive layers with strongly alkaline buffered aqueous solutions (pH of the order of to 13). Such environmental conditions will in the manner that has been previously set forth, serve to fracture the C-NH bonds in the dye coordinate structures, thus permitting coupling of the Z dye intermediates with fragments ANH at those points in the sensitized layer where actinic radiation has activated the cyanine dye structures. Where heat is thus utilized as the energizing source for bond fracturing, any convenient method may be employed for applying such heat-including irradiation of the imaging member with infra-red energy from a lamp or similar source, or heating may be accomplished through use of microwaves or the like. Following the development step, the sensitized layers of the imaging member will typically be washed in a solution of water and acetic acid (stop), bleached to remove metallic silver, fixed with conventional hypo solution, washed to remove silver complex, and thereupon the member is dried.

While the present invention has been particularly set forth in terms of specific embodiments thereof, it will be appreciated in view of the instant disclosure, that numerous variations upon the present invention are now enabled to those skilled in the art, which variations are yet in proprietary within the scope of the instant teaching. Accordingly the invention is to be broadly construed, and limited only by the scope and spirit of the claims now appended hereto.

1. A method for photographic color imaging, comprising:

(a) exposing to an image pattern a sensitized layer containing cyanine dye coordinate structures of the 14 where M is a silver ion, and ri is an integer, said structure being chosen'tobe light sensitive to a selected colorcomponent of saidlightpattern, where Z is a dye coupler for thedeveloper-colorformer fragment ANH and which when coupled with said fragment yields a dye having a desired colorrelationship to said selected color cornpo n'ent of "said incident image pattern, impingement ofjlight includ ing said selected color component servingto'reduce said silver ion and oxidize said developer fragment;

(b) disrupting the chemical bonds joining said developer fragments to said structure, whereby said dye coupler couples with said oxidized developer fragments at points exposed to said selected color component; and

(c) removing reduced metal and metal complexes from said emulsion.

2. A method in accordance with claim 1, wherein AN is a double substituted paraphenylene diamine.

3. A method in accordance with. claim 2, wherein said dye resulting from said coupling action is substantially identical in color to said selected color component.

4. A method in accordance with claim 2, wherein said dye resulting from said coupling action is substantially optically absortive of said selected color component.

5. A method in accordance with claim 2, wherein said chemical bonds are disrupted by heating said layer containing said coordinate structures.

6. A method in accordance with claim 2, wherein said chemical bonds are disrupted by treating said layer containing said coordinate structures with an alkaline solution.

7. A member for photographic color recording of a light image pattern exposed thereto, comprising:

(a) a support substrate; and

(b) a binder layer containing cyanine dye coordinate structures of the type where M is a silver ion, and n is an integer, said structure being chosen to be light sensitive to a selected color component of said light pattern, when Z is a dye coupler for the developer fragment ANH and which when coupled with said fragment yields a dye having a desired color relationship to said selected color component of said incident image pattern, impingement of light including said selected color component serving to reduce said silver ion and oxidize said developer fragment whereby disruption of the chemical bonds joining said developer fragments to said structure enables coupling of said oxidized fragments to said dye coupler at points exposed to said selected color component.

8. A member in accordance with claim 7, wherein ANH is a double substituted paraphenylene diamine.

9. A member in accordance with claim 8, wherein said dye resulting from said coupling action is substantially identical in color to said selected color component.

10. A member in accordance with claim 8, wherein said dye resulting from said coupling action is substantially optically absorbtive of said selected. color component.

11. A member in accordance with claim 8, including a plurality of species of coordinate structures of said type, each said species included in said plurality being associated with a specifically selected of said cooler components.

15 16 12. Amember in accordance with claim 11, wherein References Cited three said species arepresent, each said species being UNITED STATES PATENTS associated with a primary color of the visible spectrum. 1 3.,-A member in. accordance with claim 11, wherein each of said s cies is resent in a distinct 1a er of said p6 p y 5 RONALD H. SMITH, Prlmary Examiner 14.-A member in accordance with claim 11, wherein Us Cl X R said plurality of species are commonly present at points in a single layer. 7 96-66 R, 74, 114.1, 114.6

3,453,107 7/1969 Idelson 96-2913 

